Fluoropolymer barrier material

ABSTRACT

A novel densified fluoropolymer article is described which has a water vapor permeation of about 0.015 g-mm/m 2 /day or less, and preferably has a matrix tensile strength of at least 10,000 psi in two orthogonal directions. The articles are made by compressing expanded porous PTFE at pressures, temperatures and times which result in elimination of the pores, and subsequent stretching above the crystalline melt temperature.

FIELD OF THE INVENTION

The present invention relates to a fluoropolymer barrier material,preferably comprising a dense polytetrafluoroethylene sheet or film,which exhibits very low water vapor permeation and improved tensileproperties in both the length and width dimensions (i.e., directions),and to processes for manufacture of said barrier which include acombination of densification, sintering, and stretching ofpolytetrafluoroethylene.

BACKGROUND OF THE INVENTION

The challenge of locating a thermally stable polymer film with excellentbarrier properties as well as good mechanical properties for use in abroad range of applications has led researchers in varied directions.Both monolithic and multi-component, multi-layer films have beenconstructed; however, to date, no suitable materials have been availablewhich provide the unique combination of thermal stability, strength,thinness and, most importantly, barrier properties as demonstrated byresistance to water vapor permeation.

One attempt to solve this problem is taught in U.S. Pat. No. 6,465,103B1, to Tsai et al., which is directed to highly oriented multilayerfilms produced by coextruding or laminating at least one layer of PCTFE(polychlorotrifluoroethylene) fluoropolymer, at least one layer of apolyolefin homopolymer or copolymer and an intermediate adhesive layerof a polyolefin having at least one functional moiety of an unsaturatedcarboxylic acid or anhydride thereof. The polyolefin layer allows thefluoropolymer layer to be stretched up to ten times its length to orientthe fluoropolymer film and increase mechanical properties and watervapor properties of the film. Commercially available films of thisconstruction are sold under the trade name ACLAR® by HoneywellCorporation. However, limitations exist with respect to these materials,including the presence of the polyolefin and adhesive layers whichcontribute undesirable thickness to the final film and added cost duringprocessing. Moreover, these films have limited chemical and temperatureresistance (e.g., maximum thermal stability reported for ACLAR® films isabout 215° C.) and limited water vapor permeation resistance.

Other materials have also been evaluated for suitability in demandingbarrier applications. For example, a polyvinylidene chloride (PVDC)copolymer film sold by the Dow Chemical Company (Midland, Mich.) underthe trade name SARAN is widely known as a barrier film for protectingfoods against oxygen, moisture and chemical attack, as well as otherbarrier applications. However, this PVDC film has limited chemical andtemperature range (i.e., melt temperature of about 160° C.) and limitedwater vapor permeation resistance.

The advantage of using polytetrafluoroethylene (PTFE) in harsh chemicalenvironments and over a broad range of temperatures is well known. PTFEhas exhibited utility as a material for use in harsh chemicalenvironments where other polymers quickly degrade. PTFE also has auseful temperature range from as high as 260° C. to as low as near −273°C. However, PTFE is characterized by poor mechanical properties such aslow tensile strength, poor cold flow resistance or creep resistance,poor cut-through and abrasion resistance and a general poor mechanicalintegrity that precludes its consideration in many materials engineeringapplications.

Low porosity PTFE articles have been made in the past through use of askiving process in which solid PTFE films are split or shaved from athicker preformed article. These articles are characterized by lowstrength, poor cold flow resistance, and poor load bearing capabilitiesin both the length and width directions of the film. Processes includingpaste extrusion of PTFE fine powder have also been used to produce lowporosity PTFE articles, however they are also characterized byrelatively poor mechanical characteristics. Attempts have also been madeto strengthen low porosity PTFE films by stretching in the lengthdimension. Strength gains are minimal and, by the nature of the process,are achieved in only a single dimension, thus greatly minimizing theutility of the film.

A PTFE material, specifically, expanded polytetrafluoroethylene, may beproduced as taught in U.S. Pat. No. 3,953,566. This porous expandedpolytetrafluoroethylene (ePTFE) has a microstructure consisting of nodesinterconnected by fibrils. It is of higher strength than unexpanded PTFEand retains the chemical inertness and wide useful temperature range ofunexpanded PTFE.

However, ePTFE is porous and hence cannot be used as a barrier layer tolow surface tension fluids since such fluids with surface tensions lessthan 50 dyne-cm pass through the pores of the membrane. Compressed ePTFEarticles are taught in U.S. Pat. No. 3,953,566 in which a platen presswas used to densify a thin sheet of ePTFE with and without heat.However, cold flow occurred in the press, non-uniform parts resulted anda density of over 2.1 g/cc was not achieved. The ePTFE sheet used inU.S. Pat. No. 3,953,566 was stretched or strengthened in only onedirection and, hence, the utility of the finished article was severelylimited.

Similarly, U.S. Pat. No. 4,732,629, to Cooper et al., describes a methodof increasing the cut-through resistance of a PTFE insulated conductor.Unsintered PTFE was expanded and compressed and then applied to aconductor. However, densities of 2.1 g/cc or greater were not achieved,and the resultant tensile strengths of the finished article were notreported for either the length or width directions.

U.S. Pat. No. 5,061,561 to Katayama describes a method to produce highdensity fibers from ePTFE; however, the method yielded an article thatis significantly different from this invention and applicable only tofine filaments and not to sheets.

In U.S. Pat. No. 5,374,473 to Knox et al., a method is described forproducing articles of densified ePTFE by placing two or more layers ofporous ePTFE inside a heat and pressure stable flexible container,evacuating gas from the chamber, subjecting the chamber to a pressure of150 to 350 psi and temperature from 368-400° C., then cooling thecontainer while reducing pressure. The resulting densified structure isdescribed as useful in such barrier applications as pump diaphragms whenlaminated to a flexible backer. While the Knox et al. materials exhibitimproved barrier properties in the applications described, the methodsand articles taught are limited to making thin, flexible PTFE films withuniformly good barrier properties (e.g., a water vapor permeationcoefficient on the order of 0.10 g-mm/m²/day).

U.S. Pat. No. 5,792,525, to Fuhr et al., teaches forming creep resistantarticles which are dimensioned from a stock material of one or morelayers of expanded polytetrafluoroethylene which have been densified.The densified expanded PTFE material exhibits remnants of a fibril andnode structure, and the resultant article is resistant to creep at hightemperatures and under high loads. The stock material is preferablyformed in the manner taught in U.S. Pat. No. 5,374,473, to Knox et al.,described earlier herein. The shaped articles are then formed by anysuitable method such as a heat forming process or a machine formingprocess. Compression molding and lathing are specifically described asshaping methods. Fuhr et al. does not teach or suggest the capability offorming thin PTFE films with good barrier properties.

WO 02/102572 A1 is directed to PTFE resin blow molded articles and resinblow molding methods. The PTFE starting material is drawn by blowmolding at a temperature at or above the temperature at which PTFEbegins to melt, which is a temperature where both crystalline andnon-crystalline regions are present in the PTFE, to form a non-porousstructure. From the teachings, this method and product are subject tosignificant variations in processing and product properties, and trialand error is necessary to determine the drawing temperature and drawratio for each batch of material. In addition, significant limitationsin material size and material strength would result based on theprocessing techniques taught.

Two products currently available from W.L. Gore and Associates, Inc.include a dense fluoropolymer film exhibiting barrier properties. Thefirst product comprises a PTFE barrier layer bonded between two porousPTFE layers. The second product comprises a PTFE barrier layer bonded onone side to a thermoplastic layer such as FEP (fluoroethylenepropylene), PFA (perfluoroacrylate) or THV (a polymer oftetrafluoroethylene, hexafluoropropylene and vinylidene fluoride). Thebarrier layer in these commercial products is a film of high water vaporresistance (i.e., low water vapor permeation) PTFE having good tensileproperties in the orthogonal directions of width and length. It would beunderstood by an artisan of skill in the art that barrier performanceand bulk density of a material are positively correlated. This barrierlayer has a bulk density of 2.11 g/cc or greater, is substantially freeof pores, has a matrix tensile strength of 10,000 psi or greater in boththe width and length directions, and has a water vapor permeationcoefficient of 0.018 g-mm/m²/day. While these materials have beensuccessfully implemented in a number of applications requiring flexible,thin materials with good chemical resistance and water vapor permeationresistance, a need still exists for materials with further improvedperformance for even more demanding barrier applications.

SUMMARY OF THE INVENTION

One objective of the present invention is to provide improvedfluoropolymer barrier materials exhibiting enhanced barrier properties,including excellent water vapor permeation resistance (reported as thewater vapor permeation coefficient of the material) and strength, whichhave not heretofore been achieved in the prior art. It will beappreciated by those of skill in the art that the water vapor permeationresistance of a given material is a strong indication of permeationresistance to a wide variety of permeants, and the present invention isin no way limited thereby. Such improved barrier properties are valuablein many applications where resistance to a variety of permeants underaggressive conditions is desirable. The present invention providesimproved fluoropolymer barrier materials, preferably comprising densePTFE sheets or films, with water vapor permeation coefficients of about0.015 g-mm/m²/day or less, more preferably about 0.010 g-mm/m²/day orless, and even more preferably as low as about 0.003 g-mm/m²/day orless. As noted earlier herein, important benefits to fluoropolymerscomprising PTFE materials include a resistance to harsh chemicalenvironments where other polymers quickly degrade and a usefultemperature range from as high as 260° C. to as low as near −273° C.

Another objective of this invention is to enhance the utility of suchfluoropolymer barrier materials, preferably comprising dense PTFE sheetsor films, by providing improved tensile strengths in orthogonal (i.e.,the length and width, etc.) directions. This improvement is of utilityin applications requiring improved flex life, load bearing, impact andrupture resistance, notch propagation resistance, cut-throughresistance, and abrasion resistance. Improved tensile strengths in boththe length and width directions can be achieved in dense PTFE sheetswithout the need for reinforcing materials that compromise the chemicalperformance of the finished article. This invention provides for afluoropolymer barrier material with not only lower water vaporpermeation, but also greater tensile strengths in orthogonal directionsand greater toughness, along with the excellent chemical and thermalcharacteristics of traditional dense PTFE sheets or films. Sheets andfilms of the invention can be made in unusually thin form.

Thus, this invention now provides fluoropolymer barrier materials whichhave the unique combination of thermal stability, strength, thinnessand, most importantly, excellent barrier properties. Desirablethicknesses of the barrier materials of the present invention are on theorder of 3 mm or less, more preferably 0.5 mm or less, and even morepreferably as low as 18 μm and down to about 2 μm or less. Preferredtensile strengths of the materials of the present invention are on theorder of at least 10,000 psi in both the width and length directions(i.e., in two orthogonal directions), more preferably at least 15,000psi in at least one direction, and most preferably at least 25,000 psiin at least one direction. Throughout this document the terms width andlength are respectively analogous to the x and y directions. Barrierproperties of the novel fluoropolymer materials of the present inventionas demonstrated by resistance to water vapor permeation are about 0.015g-mm/m²/day or less, more preferably about 0.010 g-mm/m²/day or less,and even more preferably as low as about 0.003 g-mm/m²/day or less.

This invention is directed to both products and processes. The processesare processes for making sheets or films of high density PTFE, highdensity filled PTFE, and composites of high density PTFE and othermaterials, as desired, with low water vapor permeation and with hightensile strength in both the length and width directions.

These processes comprise compressing the sheet or sheets of porousePTFE, either on an appropriate batch press, such as a platen press, oralternatively, in a continuous manner by compressing between rollers orother suitable compression equipment at a linear speed and at a pressuresufficient to substantially eliminate the pores, and at a temperatureabove usual room temperature (about 20° C.). The resultant densematerial is subsequently stretched above the crystalline melttemperature of PTFE.

In one preferred aspect, the product is a sheet comprising high densityPTFE having improved permeation properties and improved tensileproperties. Specifically, the product has a water vapor permeationcoefficient of about 0.015 g-mm/m² day or less, more preferably about0.010 g-mm/m²/day or less, and even more preferably as low as about0.003 g-mm/m²/day or less, and has a matrix tensile strength of at least15,000 psi in at least one direction.

In another aspect of the invention, the product may comprise a sheet ofhigh density PTFE incorporating at least one filler and having theimproved barrier properties and other properties described.

In another preferred embodiment, the product is a sheet comprising a lowpermeation PTFE film laminated to another substrate. Lamination can beachieved by adhering or co-joining other films, e.g., by thermally,chemically or mechanically bonding the materials. Specifically, thisother substrate may include one or more fluoropolymer sheets or filmssuch as FEP, PFA, PTFE, THV and other suitable fluoropolymers.Similarly, other polymer substrate materials may include, but are notlimited to, polyurethanes, polyethylenes, polyamides, ethylene vinylalcohol (EVOH), polyvinylidene chloride (PVDC), and the like. Further,the substrate may be metallic, glass, an inorganic sheet, pressuresensitive adhesive(s), etc. Various laminated structures may be madewhich facilitate or enhance further bonding to additional layers (e.g.,textiles, or the like). The barrier component of this product has awater vapor permeation coefficient of about 0.015 g-mm/m²/day or less,more preferably about 0.010 g-mm/m² day or less, and even morepreferably as low as about 0.003 g-mm/m² day or less. Even morepreferred structures incorporate a material with these superior barrierproperties along with a tensile strength of 10,000 psi or greater inboth the x and y directions.

The process is a process for making sheets of high density PTFE, filledPTFE, or PTFE laminates with improved water vapor permeation andimproved tensile strength in both the x and y directions. One suchprocess comprises:

-   -   (a) densifying at least one sheet of expanded porous PTFE or a        bundle of layered sheets, in either sintered or unsintered form,        according to the teachings of Knox et al., U.S. Pat. No.        5,374,473,    -   (b) preheating the densified PTFE above the crystalline melt        temperature of PTFE, and    -   (c) stretching the heated PTFE membrane in the width direction,        the length direction, or both the width and length direction,        either sequentially in either order or simultaneously, at a rate        of at least 1 percent per second, more preferably at least 3        percent per second, more preferably at 5 percent per second or        greater, and at a stretch ratio of greater than 4:1. It should        be appreciated that interactions of the mechanical properties of        the precursor and the stretch rate and/or stretch ratio for        stretching performed above the crystalline melt temperature can        impact the barrier performance of the resulting material, as        demonstrated in more detail in the Detailed Description and        Examples herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart of the temperature and pressure conditions fordensification of the membranes of Example 1.

FIG. 2 is a differential scanning calorimetry (DSC) scan of a samplemade in Example 1.

FIG. 3 is a graph showing water vapor permeation coefficients for amaterial of the invention and for a range of commercially availablematerials.

DETAILED DESCRIPTION OF THE INVENTION

The objectives of this invention are accomplished by a processinvolving, in an initial step, expanding a polytetrafluoroethylene(PTFE) sheet or sheets and compressing said sheet or sheets in adirection normal to the x-y plane in order to achieve a bulk PTFEdensity of 2.11 g/cc or greater, such as is described in U.S. Pat. No.5,374,473 to Knox et al. (“Knox '473”). After compression, in a furtherprocessing step, the compressed sheet(s) are heated to a temperatureabove the crystalline melt temperature of PTFE and subsequentlystretched. The resultant sheet has greater tensile strength in thedirection of stretch than the compressed precursor from which it wasmade, has improved barrier properties as demonstrated by increased watervapor permeation resistance, and has reduced thickness, increased widthand/or increased length as dictated by the stretching operationperformed. This aspect of the invention is novel in that no one hasheretofore made a PTFE material with this unique combination ofproperties.

The sheets, or films, of expanded PTFE were made in accordance with theteachings of U.S. Pat. No. 3,953,566. In one embodiment of theinvention, an aliquot of the polytetrafluoroethylene fine powder (PTFE601A, DuPont, Wilmington, Del.) was obtained and subsequently combinedwith a lubricant (Isopar K aliphatic hydrocarbon, Exxon, Houston, Tex.).After blending, the lubricated powder was compressed into a cylindricalpellet and heat treated for a period of 18 hours. The pellet was thenextruded through a rectangular die at a reduction ratio of 70:1. Thedirection of paste extrusion is referred to as the y, or machine,direction. The resulting tape was then dried. The dried PTFE tape wasthen expanded in the y-direction between heated drums at a linear rateof greater than 10%/second, a drum temperature of about 225° C. and astretch amount equal to about 400%. The tape was then expanded in thex-direction at a linear rate greater than 10%/second, a temperature ofabout 295° C. and a stretch amount equal to about 700%. It is understoodthat this expansion may be conducted in either direction or bothdirections, either sequentially or simultaneously, utilizing apantograph machine or continuously on a tenter frame or similar machine.Suitable expansion ratios may vary significantly, such as from 1:1 to100:1, or greater and at varying expansion rates. Representative, but inno way limiting, expansion rates and ratios are included in the examplesthat follow. The films are next compressed in accordance with theteachings of Knox '473.

The densified films were then stretched at temperatures exceeding thecrystalline melt temperature of PTFE. Stretch ratios as high as 12:1were achieved at stretch rates including, but not limited to, 5% persecond. It is understood that this stretching process may be conductedin either direction, both directions either sequentially orsimultaneously utilizing a pantograph machine or continuously on atenter frame or similar machine. More specifics are noted in individualexamples.

It is believed that stretch ratios as high as 12:1, or greater, in boththe x and y directions are achievable, and one skilled in the artrealizes that the limitations associated with stretch amount are afunction of the original compressed precursor. More specifically,stretch ratio is believed to be limited by the original mechanicalproperties and thickness of the compressed precursor. The thickness ofthe compressed precursor directly impacts the ability to achieve highstretch amounts as when the compressed precursor is stretched at atemperature above the crystalline melt temperature of the ePTFE, thebulk density of the compressed precursor is increased. The stretchingresults in a reduction in unit weight and thickness. A significantincrease in the matrix tensile strength of the sheet or sheets is alsoobserved. As the following examples illustrate, matrix tensile strengthsof greater than 80,000 psi were achieved with an increase in the bulkdensity of the PTFE sheet or sheets, as demonstrated by the reduction inwater vapor permeation. It is also believed that greater matrix tensilestrengths can be achieved through greater amounts of stretch.

This invention is novel in that for the first time an extremely thin,high PTFE bulk density film with extraordinarily low water vaporpermeation coefficients and high tensile strengths in both the x and ydirections can be produced. For example, preferred thicknesses of lessthan 250 μm, more preferably less than 150 μm, even less than 50 μm, andmost preferably even less than 10 μm, can be obtained. It is notintuitively obvious that one can stretch a dense PTFE material andproduce a finished article with lower water vapor permeation, increasedstrength and without reduction in bulk density.

The novel processing technology detailed above has enabled thefabrication of a new, unique and novel PTFE sheet. As will be furtherdescribed in the following examples, this new material is a PTFE with awater vapor permeation coefficient of about 0.015 g-mm/m²/day or less,more preferably about 0.010 g-mm/m²/day or less, and even morepreferably as low as about 0.003 g-mm/m²/day or less. In addition, thesematerials preferably have a matrix tensile strength in both the x and ydirections of at least 10,000 psi, more preferably at least 15,000 psiin at least one direction, and most preferably at least 25,000 psi in atleast one direction. This material may be produced in an array oflengths and widths, and thicknesses as low as 3.5×10^(−5- inches ()0.9μm) or less have been achieved. In addition, the novel PTFE sheet may befilled with one or more fillers or incorporated in a composite sheet orsheets.

From a processing perspective this technology is unique and affords ameans of overcoming prior limitations to producing low permeabilityfilms. In summary, the value of this processing technology is theability to significantly lower the water vapor permeation of the sheetor sheets, significantly increase its matrix tensile strength and reducethickness.

The following examples are not intended to limit the scope of thisprocess or the materials that result therefrom.

Test Methods and Process Metrics

Water Vapor Permeability Testing and Water Vapor Permeation CoefficientDetermination

Determination of the water vapor permeability of the materials wascarried out in accordance with ASTM F-1249 by MOCON, Inc. (Minneapolis,Minn.).

Specifically, the instrument used to test the water vapor permeation ofthe materials was a MOCON Permatran W 3/31 (MOCON/Modern Controls, Inc.,Minneapolis, Minn.). The permeant used was 100% RH water vapor (49.157mmHg), the carrier gas was 100% nitrogen, dry, at ambient pressure andthe temperature at which the test was carried out was 37.8° C.

Test samples were cut to approximately 10 cm by 10 cm, affixed in theinstrument diffusion cell and conditioned according to the instructionsfor the MOCON Permatran W 3/31. Water vapor transmission rate, or watervapor permeability, was reported by the instrument in g/m²/day.

The water vapor permeation coefficient of each sample was calculated bymultiplying the water vapor transmission rate by the thickness of thetest sample. Results are reported as g-mm/m²/day.

Matrix Tensile Strength Testing

All specimens were tested according to ASTM D 882-90. A 20 in./min. (508mm/min.) cross-head speed, 2 inch (51 mm) gauge length and rectangularspecimen of at least 5 inches (127 mm) in length were employed.

The quantity matrix tensile is a means of expressing the maximum loaddeveloped during the test as a function of the cross-sectional area ofmaterial in the specimen. This provides a means of accurately comparingtensile strengths among PTFE-based specimen of varying density orporosity by normalizing the stress at maximum load with respect to thecross-sectional area of the PTFE within the sample.

Specifically:Matrix Tensile (psi)=Max load (lb.)/X−sect area PTFE (in.²)

-   -   where, Max load=Maximum load specimen generates during testing        x-sect area PTFE (in.²)=gperft/(12×P×2.54³)=gperft×2.3×10⁻³    -   where gperft=specimen unit weight in grams per 1 foot        P=Mean intrinsic density of PTFE=2.18 g/cc        Therefore Matrix Tensile (psi)=Max Load (lb.)/(gperft×2.3×10⁻³)        Similarly, Matrix Tensile (Mpa)=Matrix Tensile (psi)×6.89*10⁻³        Differential Scanning Calorimetry (DSC)

This test is performed using a TA Instruments Q1000 DSC and TAInstruments standard aluminum pans and lids for DSC. A TA InstrumentsSample Encapsulation Press was used to crimp the lid to the pan. Weightmeasurements were performed on a Sartorius MC 210P microbalance.

One pan and lid were weighed on the balance to 0.01 mg precision. Usinga 6.0 mm die punch, enough discs of the test sample material were addedto the pan to constitute 6 mg, again recorded to 0.01 mg precision.These values were entered into the Thermal Advantage control softwarefor the Q1000. The lid was placed on the pan and was crimped using thepress. Care was taken to ensure that no sample material was caught inthe crimp between the lid and the pan. A similar pan for reference wasprepared, with the exception of the sample article, and its weight wasalso entered into the software. The pan containing the sample articlewas loaded onto the sample sensor in the Q1000 and the empty pan wasloaded onto the reference sensor. The samples were then subjected to thefollowing thermal cycling steps:

-   1) Equilibrate at −50.00° C.-   2) Ramp 20.00° C./min to 360.00° C.-   3) Isothermal for 5.00 min-   4) Mark end of cycle-   5) Ramp 20.00° C./min to −50.00° C.-   6) Mark end of cycle-   7) Ramp 20.00° C./min to 420.00° C.-   8) Mark end of cycle-   9) End of method    Data was analyzed, unaltered, using Universal Analysis 2000 v.3.9A    from TA Instruments. Data from the scan indicated in step 7 were    analyzed.

EXAMPLES Example 1

A 240 lb. aliquot of PTFE fine powder (PTFE 601A, DuPont, Wilmington,Del.) was combined with 44.16 lb. of lubricant (Isopar K, Exxon,Houston, Tex.), subsequently blended, compressed into a cylindricalpellet, and thermally conditioned for 18 hours at a temperature of 49°C. The cylindrical pellet was then extruded through a rectangular die ata reduction ratio of 70:1. The resultant tape was then dried in order toremove the lubricant.

The dried PTFE tape was then expanded in the y-direction between heateddrums at a linear rate of greater than 10%/s, a drum temperature of 225°C. and stretch amount equal to 400%. The tape was then expanded in thex-direction at a linear rate greater than 10%/s, a temperature of about295° C. and stretch amount equal to 700%. The resulting product was anunsintered ePTFE membrane.

In order to determine the effect of sintering on the water vaporpermeability of membranes, a portion of this unsintered ePTFE membranewas restrained and subsequently sintered so that two membranes, onesintered and one unsintered, could be subjected to further processing.By “sintering” is meant subjecting the material to a temperature abovethe crystalline melt temperature of PTFE. Sintering of the one membranewas accomplished by exposing the membrane to a temperature of 375° C.for 220 seconds by passing it through an oven. No additional expansionwas imparted during the sintering operation.

The two resulting membrane precursors, one sintered and one unsintered,were densified according to U.S. Pat. No. 5,374,473 Knox, et al.Specifically, four plies of the unsintered membrane with a nominalthickness of 0.013 inch (330 μm) and five plies of the sintered membranewith a nominal thickness of 0.008 inch (203 μm) were placed between twocaul plates in an autoclave bag assembled from polyimide film (DuPont'sKAPTON®). The assembly was placed in an autoclave (Vacuum PressInternational Series 24), vacuum was drawn in the bag and the pressureand temperature of the autoclave were gradually raised based upon thetemperature and pressure conditions summarized in FIG. 1. The resultantcompressed ePTFE sheets, one sintered and one unsintered, wereapproximately 0.010 inch thick. Samples of each of the sintered andunsintered forms of this intermediate PTFE were tested for water vaporpermeation and were found to be 0.1 and 0.127 g-mm/m²/day, respectively.

The resultant compressed articles were then placed in a pantographmachine wherein the material was heated above the crystalline melttemperature of PTFE by exposure to air temperature of about 370° C. fora period of 20 minutes. The samples, while still heated, were thenstretched in the x-direction or simultaneously in both the x andy-directions at stretch amounts of up to 1100% and a stretch rate of 5%per second for each direction. Processing conditions are summarized inTable 1. As shown in Table 1, for each of the sintered and unsinteredmembranes, two melt stretch conditions were performed. Four testspecimens were analyzed from each combination of sintering condition andmelt stretch processing. Note that a two-pass process wherein the resultof the first melt stretch operation was used as the precursor of thesecond stretch was used to produce these embodiments.

The samples were then subjected to Water Vapor Permeability testingusing the procedure described above herein. Table 2 summarizes the watervapor permeation coefficients, matrix tensile strengths, thicknesses andpercent crystallinity for the various samples.

A sample processed according to processing condition “D” identified inTable 2 was evaluated thermally using Differential Scanning Calorimetry,and the resulting scan for this sample is shown in FIG. 2. TABLE 1Process Conditions for Samples of Example 1 Transverse Machine DirectionDirection Melt Melt Example Stretch Stretch 1^(st) Pass 1^(st) Pass2^(nd) Pass 2^(nd) Pass ID (TDMS) (MDMS) PTFE TDMS MDMS TDMS MDMS NumberRatio Ratio Precursor Ratio Ratio Ratio Ratio A-1 9 3 Non-Sintered 3 3 31 A-2 9 3 Non-Sintered 3 3 3 1 A-3 9 3 Non-Sintered 3 3 3 1 A-4 9 3Non-Sintered 3 3 3 1 B-1 12 3 Non-Sintered 3 3 4 1 B-2 12 3 Non-Sintered3 3 4 1 B-3 12 3 Non-Sintered 3 3 4 1 B-4 12 3 Non-Sintered 3 3 4 1 C-19 3 Sintered 3 3 3 1 C-2 9 3 Sintered 3 3 3 1 C-3 9 3 Sintered 3 3 3 1C-4 9 3 Sintered 3 3 3 1 D-1 12 3 Sintered 3 3 4 1 D-2 12 3 Sintered 3 34 1 D-3 12 3 Sintered 3 3 4 1 D-4 12 3 Sintered 3 3 4 1

TABLE 2 Properties of Samples of Example 1 Water Permeation TensileCoefficient Strength - Tensile Example (g * mm/ Length Strength - ID -m{circumflex over ( )}2/day) Direction Width Direction Thickness A-1.0042 30420 psi 71360 psi 9.0 μm A-2 .0056 32500 67600 9.0 A-3 .004231800 64920 9.0 A-4 .0040 30190 68940 9.0 B-1 .0037 26890 88880 8.5 B-2.0024 24760 91910 8.5 B-3 .0021 24870 91660 8.5 B-4 .0024 28780 869108.5 C-1 .0054 29000 63670 14.0 C-2 .0091 30440 63800 14.0 C-3 .010329340 65340 14.0 C-4 .0054 28970 62540 14.0 D-1 .0043 24640 78060 13.0D-2 .0043 25790 76910 13.0 D-3 .0039 23610 80460 13.0 D-4 .0036 2650075310 13.0

Example 2

A laminate of dense PTFE and perfluoroacrylate (PFA) was made in thefollowing manner. Specifically, a PTFE material was made according tothe processing conditions noted for the “A” samples described in Example1, using a two-pass stretching operation. Following the second passstretching, the heater was removed from the pantograph. While thestretched PTFE barrier film remained on the pantograph pin body, a PFAfilm (Part No. 100 LP, 0.001 inch (25 μm) thick, from DuPont,Wilmington, Del.) was placed on one side of the PTFE barrier film. Thetwo films were then subjected to a temperature of 370° C. for 5 minutesto form a laminate of PTFE barrier film and PFA.

Example 3

An unsintered expanded PTFE material was made and densified according toU.S. Pat. No. 5,374,473 Knox, et al. as described in Example 1, exceptthat only a single ply of the unsintered material was subjected to thedensification step. The resulting densified material was then stretchedaccording to the processing conditions “A” described in Example 1. Theresulting PTFE barrier film had a thickness of 0.1 mils (2.5 μm) and awater vapor permeation coefficient of 0.007 g-mm/m²/day.

Example 4

An unsintered expanded PTFE material was made and densified according toU.S. Pat. No. 5,374,473 Knox, et al. as described in Example 1, exceptthat only two plies of the unsintered material were subjected to thedensification step. The resulting densified material was then stretchedaccording to the processing conditions “B” described in Example 1. Theresulting PTFE barrier film had a thickness of 0.1 mils (2.5 μm) and awater vapor permeation coefficient of 0.003 g-mm/m²/day.

COMPARATIVE EXAMPLE

In an attempt to roughly assess the relative water vapor permeationcoefficient of the material of the present invention versus commerciallyavailable fluoropolymer materials, a series of commercially availablefluoropolymer films was evaluated. Four samples of each of the followingfilms were sent to MOCON, Inc. for determination of water vaporpermeation coefficient, and the results are shown graphically in FIG. 3:Material Source ACLAR ULTREX ® 2000 film Honeywell Corporation ACLARULTREX ® 3000 film Honeywell Corporation DEWAL 200T ® film (2 mil) DeWALIndustries DEWAL 220T ® film (2 mil) DeWAL Industries DEWAL 502T ® film(2 mil) DeWAL Industries FEP (2 mil) DuPont PFA (2 mil) DuPontComparison was made in FIG. 3 with sample D-4 of Example 1.

1. An article comprising an expanded PTFE film having a water vaporpermeability coefficient of about 0.015 g-mm/m²/day or less and a matrixtensile strength of at least 10,000 psi in two orthogonal directions. 2.The article of claim 1, wherein said film has a matrix tensile strengthof at least 15,000 psi in at least one direction.
 3. The article ofclaim 1, wherein said film has a matrix tensile strength of at least25,000 psi in at least one direction.
 4. The article of claim 1, whereinsaid film has a water vapor permeability coefficient of about 0.010g-mm/m² day or less.
 5. The article of claim 1, wherein said film has awater vapor permeability coefficient of about 0.003 g-mm/m²/day or less.6. The article of claim 1, wherein said film further contains a filler.7. The article of claim 1, wherein said expanded PTFE film has athickness of 250 micrometers (μm) or less.
 8. The article of claim 1,wherein said expanded PTFE film has a thickness of 150 micrometers (μm)or less.
 9. The article of claim 1, wherein said expanded PTFE film hasa thickness of 50 micrometers (μm) or less.
 10. The article of claim 1,wherein said expanded PTFE film has a thickness of 10 micrometers (μm)or less.
 11. The article of claim 1, wherein said expanded PTFE film hasa thickness of 5 micrometers (μm) or less.
 12. The article of claim 1,wherein said expanded PTFE film has a thickness of 1 micrometer (μm) orless.
 13. A laminate comprising: (a) an expanded PTFE film having awater vapor permeability coefficient of about 0.015 g-mm/m² day or lessand a matrix tensile strength of at least 10,000 psi in two orthogonaldirections; and at least one substrate.
 14. The article of claim 13,wherein said film has a water vapor permeability coefficient of about0.010 g-mm/m² day or less.
 15. The laminate of claim 13, wherein saidsubstrate comprises a fluoropolymer.
 16. The laminate of claim 13,wherein said substrate comprises PFA.
 17. The laminate of claim 13,wherein said substrate comprises FEP.
 18. The laminate of claim 13,wherein said substrate comprises THV.
 19. The laminate of claim 13,wherein said substrate comprises PTFE.
 20. The laminate of claim 13,wherein said laminate comprises the expanded PTFE film oriented betweentwo substrates.
 21. The laminate of claim 13, wherein said substratecomprises PCTFE.
 22. The laminate of claim 13, wherein said substratecomprises at least one material selected from the group consisting ofpolyurethane, polyethylene, polyamide, EVOH and PVDC.
 23. The laminateof claim 13, wherein said substrate comprises at least one pressuresensitive adhesive.
 24. The laminate of claim 13, wherein said substratecomprises at least one textile.
 25. The laminate of claim 13, whereinsaid substrate comprises metal.
 26. The laminate of claim 13, whereinsaid substrate comprises glass.
 27. The laminate of claim 13, whereinsaid substrate comprises an inorganic sheet.
 28. A method of making apolytetrafluoroethylene (PTFE) film having a water vapor permeabilitycoefficient of about 0.015 g-mm/m²/day or less, the method comprisingthe steps: (a) preparing of a biaxially expanded PTFE film; (b)densifying said expanded PTFE film; (c) stretching the densifiedexpanded PTFE film at a temperature exceeding the crystalline melttemperature of PTFE.
 29. The method of claim 28, wherein the expandedPTFE film is sintered prior to step (b).
 30. The method of claim 28,wherein said biaxially expanded PTFE film comprises two or more plies ofexpanded PTFE.
 31. The method of claim 28, wherein said steps arecarried out in a continuous manner.